The ability to design and construct 
solid-state materials with pre-determined structures is a grand challenge in 
chemistry. An inventive strategy based on reticulating 
metal ions and organic 
carboxylate links into extended networks has been advanced to a point that has allowed the design of porous structures in which pore size and functionality can be varied systematically. MOF-5, a prototype of a new class of porous materials and one that is constructed from octahedral Zn—O—C clusters and 
benzene links, was used to demonstrate that its 3-D 
porous system can be functionalized with the organic groups, —Br, —NH2, —OC3H7, —OC5H11, —H4C2, and —H4C4, and its pore size expanded with the long molecular struts 
biphenyl, tetrahydropyrene, 
pyrene, and 
terphenyl. The ability to direct the formation of the octahedral clusters in the presence of a desired 
carboxylate link is an essential feature of this strategy, which resulted in the design of an isoreticular (having the same framework topology) series of sixteen well-defined materials whose crystals have open space representing up to 91.1% of the 
crystal volume, and homogeneous periodic pores that can be incrementally varied from 3.8 to 28.8 angstroms. Unlike the unpredictable nature of 
zeolite and other 
molecular sieve syntheses, the deliberate control exercised at the 
molecular level in the design of these crystals is expected to have tremendous implications on materials properties and future technologies. Indeed, data indicate that members of this series represent the first monocrystalline mesoporous organic / inorganic frameworks, and exhibit the highest capacity for 
methane storage (155 cm3 / cm3 at 36 atm) and the lowest densities (0.41 to 0.21 g / cm3) attained to date for any crystalline material at 
room temperature.